Water repellent and process of making same



Patented 28, 1941- UNITED S'l'A'lES PATENT- ol -"r cs -wsmmmmannnocsssor msxmosm' John D. But, West Orange. $1., adgnorto oorpotaflo Ellis-Foster Company, a

Jersey an organic acid anion radical and the group de-' noted by N(tert.) is a tertiary amine such as pyridine, quinoline, triethanolamine or trimethylamine.

An object of the invention is to provide readily water dispersible materials which whenapplied to textile fibers and thereafter decomposed on the fibers will render them distinctly water repellent.

I have found that these materials may be readily synthesized from aldehydes, the acid chlorides of the higher fatty acids such as stearlc, palmitlc and lauric acids. and a tertiary amine. The acid chlorides may be formed in any convenient manner such as treatment of the acid or alkali metal soap with phosphorus trichloride, phosphorus pentachloride, or thionyl chloride. I have further found that if thionyl chloride is employed I may coreact the fatty acid, aldehyde such as formaldehyde in the form of its waterfree polymers and thionyl chloride to obtain the chloralkyl ester of the acid. When this is treated with pyridine a material of the general formula given above is secured. In the event that the acid chloride isavailable or initially prepared, the quaternary ammonium compounds may be secured by reacting together the amine, acid chloride and aldehyde until water-soluble materials are obtained. ferred but other aldehydes than formaldehyde can be employed such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde. A further modification is that in some cases it has been found possible to use mixed anhydrides such as vstearoaeetic anhydride, lauropropionic anhydride and so forth in place of the acid chloride in the above reaction. The latter products correspond to the general formula wherein X is the radical of a weak water-soluble organic acid.

p'erature.

nofNew No Drawing. Application July 19, 1939, Serial N .45

v o. 385 7 Claims. (CL 260-295 The following examples are given to. illustrate the process of the present invention. all proportions being in parts by weight.

Example 1.'-00 parts of stearyl'chloride were heated with 12 parts of paraformaldehyde on a steam bath at 90 C. for 4 hours. In this time the formaldehyde slowly dissolved, reacting with the stearyl chloride to -produce .a substantially odorless, low melting waxy chloromethyl stearate. 33.3 parts of chloromethyl stearate were treated with 1.9 parts of pyridine and warmed for several hours at 45 C. On allowing the material to stand at room temperature in tightly stoppered bottles for several weeks, the odor of pyridine disappeared and the stearoyl-oxymethyl pyridlnium chloride which resulted was readily water dispersible.

Example 2.32.7 parts of lauryl chloride were mixed with 4.5 parts of paraformaldehyde and 11.8 partsof pyridine. The mixture was heated on a steam bath at 90 C. until the lauryloxymethyl pyridinium chloride was readily water mixed with 12 parts of pyridine and 4.6 parts of paraformaldehyde. The mixture was heated on a steam bath at 90 C. for 4 hours, resulting in Formaldehyde is pre- -a readily water dispersible'oleyloxymethyl pyridinium chloride.

Example 4.30.2 parts of stearyl chloride, 4.4 parts of paraldehyde and- 7.9 parts of pyridine were heated on a steam bath at -100 C. for 6 hours. In this time a-stearoyloxyethyl pyridinium chloride was formed which was readily solubl'e in water to form strongly foaming solutions.

Example 5.51.2 parts of palmitic acid, 6 parts of paraformaldehyde and 23.6 parts of thionyl chloride were heated together slowly up to 90 C. on a steambath. To the chloromethyl palmitate which had been formed, 15.8 parts of pyridine were added, when evolution of sulphur dioxide and hydrogen chloride had ceased. The solution which resulted was bottled and tightly stoppered, then heated at 60 C. for 48 hours. A slow reaction with the pyridine occurred and the originally liquid material slowly solidified.

In order to secure the lighest colored quaternary ammonium compounds'of this invention it is desirable to work at as low temperatures as possible. It has been found that in the first place light colored chlorom'ethyl esters may be produced by the simultaneous reaction of thionyl chloride with an acid and formaldehyde or. its polymers. In producing the quaternary ammonium derivative, the least darkening is caused by reacting the a-chlOlO ester with a tertiary amine somewhat below C. and in the case of pyridine preferably within the range of 50-70 C.

60 Example 6.85.2 parts of stearlc acid, 9 parts ceased. The chloromethyl stearate was cooled to' room temperature and 23.7 parts of pyridine added. The solution was heated at 60 C. for 48 hours, resulting in a pure white, hard waxy stearoyloxymethyl pyridinium chloride. The stearoyloxymethyl pyridinium chloride was recrystallized twice from a mixture of ethyl acetate and ethyl alcohol. The crystals were found to have a melting point of 93-94 C.

Example 7.85.2 parts of stearic acid, 18 parts of acetic acid, 9 parts of paraformaldehyde and 35.4 parts of thionyl chloride were heated together at 90 C. under a reflux condenser for 4 hours until fumes were no longer given ofi. The pale yellow liquid was cooled to room temperature, mixed with 23.7 parts of pyridine and placed in a closed container. It was then heated at 60-'I0 C. for 72 hours, resulting in a white waxy stearoyloxymethyl pyridinium acetate.

Example 8.-11.1 parts of chloromethyl stearate (formed as in Example 1) were warmed at 40 C. with parts of triethanolamine for about minutes. A pale, hard, waxy stearoyloxymethyl triethanol ammonium chloride was secured. This material was very readily dispersible in water.

The materials described in the foregoing examples are all readily dispersible in water and as water solutions may be used to impregnate textile materials. The treated textiles (e. g., cotton, linen, rayon, acetate, wool, and silk) are dried at substantially below 100 C., preferably below about 60 G. Then the materials are heated at above about 100 C. in order to decompose the quaternary ammonium salts in the fibers. The following is a tabulation of the materials in the above examples and the effect imparted to textile sisting of hydrogen, alkyl,

The above examples are not limiting to the scope of this invention in" any way, since numerous modifications may be made in the long chain fatty acid, aldehyde, tertiary amine and halogen or organic salt-forming acid.

What I claim is:

1. Stearoyloxymethyl pyridinium chloride.

2. Alpha-stearoyloxyethyl pyridinium chloride.

3. Stearoxymethyl pyridinium acetate.

4. A compound of the general formula RCOO-CHR'-N(tert.)X, wherein R is an 'alkyl radical containing not less than 10 carbon atoms, R is selected from the group consisting of hydrogen, alkyl, aryl and aralkyl groups, N(tert.) is a tertiary amine and X is selected from the group consisting of halogens and anion radicals of water-soluble carboxylic acids, said compound being capable of rendering cellulosic textile materials water-repellent.

5. The process of making a compound of the general formula RCOOCHR -N(tert.)X, wherein R is an alkyl radical of not less than 10 carbon atoms, R is selected from the group conaryl and aralkyl groups, N (tert.) represents a tertiary amine and X is selected from the group consisting of halogens and organic acid anion radicals, said compound being capable of rendering fabrics waterrepellent, which comprises reacting a compound RCOX with an aldehyde R CHO and further treating the intermediate with a tertiary amine.

6. The process of making a compound of the formula RCOOCHR N(tert.) Cl, wherein R is an alkyl radical of not less than 10 carbon atoms, R is selected from the group consisting of hydrogen, alkyl, aryl and aralkyl groups, and- N (tert.) represents a tertiary amine, said compound being capable of rendering fabrics watercotton by them: repellent, which comprises reacting thionyl chlo- .2 5 Material P823351; ffifgg Dried at- Baked at- Remarks 1 Stgargyloxymethylpyridiniumchlo- 2 0.66 Bogg tempera- 120 C.6min--- Ex l l elgit mtetr repellency. No ten- 2 Lgiialoxymethyl pyridinium chlo- 2 0.66 do 100C.10min.:. Do. 3 olgz l oxymethyl pyridinium chlo- 2 0.66 Do. 4 a-gfisarriggloxyethyl 'pyridinium 2 0.66 ....do --do Do. 5 Pa l n ig tfigxymethyl pyridinium 1 033 --do 0 G.6min..--- Biggi 1 13. i: 232%; s ggr iy solution. 6 Eltaargglozymcthyl pyridinium 2 0.06 .do 120 0.10inin--- Efizellilnelglt) 21531;] repellency. No ten- 7 Btwloxymethyl pyridinium 2 I None do 140 0.10min.-- Do. 8 Btearoyloxymethyl trietlianol am- 2 None -do.------ 120O.5min. Do.

monium chloride.

In the above table sodium acetate was employed as the neutralizing agent in some cases; however, other salts of weak acids may also be used. In this way the textiles are not tendered on baking and on washing possess a soft feel not present in the untreated cloth. When the stron er tertiary amines such as trimethylamine, triethanolamine and the like are employed no neutralizing agent need be used. On the other hand, by the use of weak organic acids such as acetic, formic, succinic, phthalic and the like to form the mixed ester of the hypothetical methylene glycol and subsequent treatment of the mixed ester with a tertiary amine to form the quaternary ammonium salt, no further neutralizing agent is found to be necessary.

ride with an acid RCOOH and an aldehyde R CHO, and treating the intermediate with a tertiary amine.

'7. The process of making a compound of the formula RCOOCHR N(tert.)0COR where- 

